Removal of 2-methyl butene-1 from petroleum resin feeds



Dec. 19, 1961 J. B.R1LEY ETA.

REMOVAL OF Z-METHYI.. BUTENE-l FROM PETROLEUM RESIN FEEDS Filed May 8, 1958 quality petroleum resins.

United States Patent C) 3,014 012 REMOVAL F Z-METHYL BUTENE-l FROM PETROLEUM RESIN FEEDS John B. Riley, Westfield, and Howard T. Oakley, Eliza- This invention relates to the preparation of improved petroleum resins from steam-cracked petroleum streams. More particularly, it relates to the process for preparing resins from steam-cracked light naphtha streams containing substantial amounts of C components, wherein the resin quality is improved by removing the 2 -methyl butene-l from the stream-cracked resin feeds.

Until now, the petroleum resins of the type described herein have been produced largely from the steam-cracked heavier petroleum fractions boiling in the range of about 250 to 700 F., such as heavy naphtha, kerosene, gas oil, and the like. These heavier fractions are cracked in the presence of 50-90 mol percent steam at temperatures of about 1000 to 1500 F. to give highly unsaturated products. 'I'he liquid cut boiling from about .60 F. up to 400 F. and higher, containing large proportions of C5 to C9 olens and diolelins, is then polymerized over a Friedel-Crafts catalyst to produce the ldesired petroleum resins. The preparation of such resins has been described in U.S. Patent 2,734,046.

More recently, however, light naphthas have been used frequently as steam-cracking feed stocks in place of the heavier naphthas, gas oils and the like. While the steam cracking of such light naphthas has been quite successful in producting ethylene, butadiene, and the like, there has been considerable difficulty in the satisfactory preparation of petroleum resins from the C5-25 0 F. fraction obtained from suchy steam-cracked light naphthas, These difficulties have been alleviated by following the procedures described in application Serial No. 627,090. That is, resin production may be improved by steam-cracking a light naphtha boiling from about 120 to 350 F., and subjecting the steam-cracked fraction boiling from about 60 F up to about 120 F., i.e. the initial boiling point of the light virgin naphtha, to polymerization. However the softening point o-f the resins produced from the steamcracked light naphthas are still rather low in comparison to the resins produced from the steam-cracked heavier fractions.-

It is the chief object of this invention to produce resins having softening points higher than have been heretofore possible, from steam-cracked distillates largely comprising C5 components. It is a more specific object to upgrade the C5 or C5C6 fraction obtained from a steamcracked light naphtha in order to polymerize it into high These and other objects will become more clearly apparent from the following description of the nature, scope, and operation of the invention.

It should be understood that all ratios, proportions, and percentages are expressed throughout on a weight basis, unless otherwise indicated.

It has now been found that the softening point` of the petroleum resin prepared from steam-cracked fractions containing high proportions of C5 components may be substantially increased without serious loss in yield by removing substantially all of the 2methyl butene-l from the feed fraction. This removal may be brought about by fractionally distilling ofic a close fraction containing the Z-methyl butene-l which boils normally at 88 F. For example, the 86 to 90 F. cut will normally contain substantially all of the 2-methyl butene-l. The fraction removed may be passed over a dehydrogenation catalyst, converting the Z-methyl butene-l to isoprene, piperylene,

C 3,014,012 ce Patented Dec. 1 9, 1 961 and other more highly unsaturated hydrocarbons, which may be added back to the resin feed to further increase resin yield and softening point. Alternatively, instead of fraction distillation, the entire C5-containing fraction may be passed over the dehydrogenation catalyst.

The present invention is adaptable and advantageous to processes for preparing resins from any petroleum fraction containing substantial proportions of Z-methyl butenel, but the invention is most especially advantageous to the preparation of resins from steam-cracked light naphthas, since, as seen in Serial No. 627,090, the most suitable resin-producing fraction available in such crackednaphthas is the C5 or C5-C5 cut. Therefore a more thorough study of such cracked naphtha feeds in comparison with steam-cracked fractions having lower C5 contents will aid in the better understanding of this invention. The composition of a typical C5 steam cracked naphtha cut is represented below by a 60-120 F. cut of a steamcracked Kuwait light naphtha,-which, before cracking, boils from about 120 to 220 F. This steam-cracked naphtha `cut is compared with a typical resinification feed comprising a lO0-2'48 F. cut from a steam-cracked gas oil.

TABLE I C5 cut steam- 10W-248 F. cracked Kucut of steam- Component Wait light cracked gas naphtha, oil Weight weight perpercent cent Cs cut:

Isoprene 7. 7 0. 3 Piperylene 6. 1 9. 8 Cyclopentadiene 3. 3 0. 3

Total diolens 17. 1 10. 4

Pentene-l 1S. 4 nil Pentene-2 15. 7 1.8 2-Methyl butene-l.. 14. 4 nil B-Methyl butene-l 1. 2 nil 2-Methyl butene-Z.. 6.5 2.

Cyclopentene. 3. 2 2.

Total olenns 59.4 7.

Total parafins 23. 3 2.

5 'lotal C1 cut 0 44.

TotalCs-lout 0 13.

Cyclodienes have been substantially removed from both of the fractions shown in Table I. 14.4% of the C5 steam-cracked light naphtha fraction consists of Z-methyl butene-l, whereas only negligible In one embodiment of this invention, a C5 steamcracked light naphtha'st'ream boiling from aboutA 60 to 120 F. is passed through a fractional distillation tower, i

and a fraction boiling between 86 and 90 F. is separated from the C5 stream. The remaining C5 stream comprises the feed to the polymerization zone.

The polymerization is carriedA out at temperatures between 40 to -|-160 F., preferably vat 75 to 110 F., using about 0.25 to 3%, preferably l to 1.5% of a Friedel-Crafts catalyst based on cracked naphtha being treated. The catalyst may be used either as a finely divided solid, or as a solution in methyl or ethyl chloride, or as a hydrocarbon slurry, etc. For instance, the polymerization may be effected by adding 1% powdered the mixture at F. for two hours. The polymerization is usually carried out at atmospheric pressure, |but at It is observed that the higher temperatures it is desirable to increase the pressure suiciently to keep the monomers in the liquid phase. Accordingly, when polymerizing at 160 F. a pressure of about atmospheres is desirable. Upon completion of the reaction the catalyst is destroyed by adding water or methyl alcohol or the like. The catalyst and quenching medium is separated from the resin-containing hydrocarbon solution and the resin solution washed with water, caustic, an aqueous solution of sodium carbonate or the like. The resin raiiinate or stabilized naphtha is next distilled from the resin solution at atmospheric pressure and the remaining ll material is finally removed by vacuum distillation. The desired hydrocarbon resin constitutes the bottoms from this final distillation. The yield and softening point are largely dependent upon the severity of this final stripping step, with the yield decreasing and the softening point increasing with increasing severity of stripping.

The fraction boiling between about 86 and 90 F. may be recovered from the fractional distillation zone and passed to a dehydrogenation stage. In such a stage, the fraction is contacted with a metal oxide dehydrogenation catalyst such as iron oxide, magnesium oxide, and the like, at temperatures of about 1100 to 1225 F., preferably 1200 to 1225 F., for contact times suflicient to convert substantially all of the 2-methyl butene-l to isoprene, e.g. usually about to 35 seconds. The total dehydrogenated fraction may be charged to the polymerization zone to increase the resin yield, or the isoprene may be first separated from the dehydrogenated fraction by fractional distillation for use in other manufacturing processes and the remaining components charged to the polymerization zone. If isoprene is charged to polymerization, not only is the resin yield increased, but the softening point as Well.

Alternatively, under controlled conditions, the entire steam-cracked fraction may be subjected to dehydrogenation, thereby eliminating the fractional distillation step. The dehydrogenated product would be enriched in isoprene thereby leading to the production of resins of higher softening point.

A specific embodiment of the invention will now be d..- scribed with reference to the attached diagram. The fraction boiling above 59 F. of a steam-cracked light naphtha stream is introduced by line 1 into fractional distillation tower 2. The fraction boiling up to 122 F. is removed overhead via line 3, a portion of this overhead stream being returned to still 2 as reflux via line 4. The fraction boiling above 122 F. is withdrawn as bottoms via line 5 and is recycled inpart via line 6. Alternatively, tower 2 may be operated so as to recover several side-stream cuts boiling above 122 F., such as a 122- 168 F. cut and a l69194 F. cut, leaving a 194-lcut as bottoms.

It is often desirable to dimerize by heat soaking and remove by distillation the cyclodienes present in the cracked distillate. In the present invention, this step could be performed upon the initial 59 F.I fraction or, upon the separated 59-122 F. fraction. This heatsoaking procedure, e.g., at 220F. for 5 hours, to dimerize cyclopentadienes, is described fully in U.S. Patent 2,734,046. The presence of cyclodienes, as stated previously, tends to degrade somewhat the resin color and stability.

The 59122 F. fraction is passsed to a second fractionation tower 10, where the fraction boiling between 59 and 86 F. is recovered overhead via line 11. Part of the 59 86 F. cutis returned as reflux via line 12. A side-stream fraction boiling from 86 to 90 F. is withdrawn via line 13, part of this stream also being returned as refiux via line 14. The bottoms cut boiling from 90 to 122 F. is withdrawn through line 15, with a portion being returned to tower 10 via line 16. The overhead 59-86 cut and the bottoms 90-122 cut are combined and passed via line 17 to polymerization zone 20.

The 86-90 F. side-stream cut contains substantially all of the 2-methyl butene-l present in the initial feed to tower 2. If desired, this narrow boiling fraction may be subjected to dehydrogenation to convert the 2-methyl butene-l to isoprene and other diolens. The resulting stream may be combined with the polymerization feed in line 17, or the isoprene may be recovered and purified for use in other valuable operations.

The polymerization is conducted in reactor 20 at a temperature between and 110 F. in the presence of 0.5 to 2% aluminum chloride catalyst, the catalyst being introduced via line 21. Agitation is provided by stirrer 22, and the residence time in the reactor is about 1 to 3 hours. The resulting admixture is passed via line 23 to tank 25 where the residual catalyst is quenched at 180 to 220 F. by the addition of water containing a nonionic wetting agent through line 26. Agitation is provided by stirrer 27. Catalyst is removed in the aqueous phase via line 2S and the reaction mixture is passed via line 29 to scrubber 30. A 10% aqueous solution of 10 wt. percent NaZCOa is passed into scrubber 30 via line 31, and agitation is provided by stirrer 32 at 300 to 360 F. The aqueous phase is removed via line 33, and the scrubbed resin solution is passed via line 34 to atmospheric distillation column 35.

In column 35, the reaction mixture is distilled to a liquid temperature of about 350 to 400 F. to strip the unreacted hydrocarbons from the mixture via line 36. A portion of these unreacted hydrocarbons is recycled as redux via line 37. The crude resin solution is then passed via line 38 to vacuum or steam distillation tower 40, where, at conditions of or equivalent to a top temperature of 480 to 520 F. at 2-10 mm. Hg, the liquid polymer or fill is stripped overhead via line 41, with a portion being reliuxed via line 42, andthe finished resin is recovered as bottoms from line 43. If steam is employed, the steam is introduced via line 44. The softening point of the final resin is largely dependent, up to certain limits, upon the severity of this final stripping step.

The invention will be further illustrated, but not limited, by the following examples.

Example 1 A blend of C5-C steam-cracked petroleum fractions, having an initial boiling point of 60 F. and from which the .cyclodienes had been substantially removed following a dimerization step, had the following composition:

The above analysis shows that the olefin-diolefin ratio of the above blend was about 3.4, and that, with respect to the C? components, the composition of the blend was almost identlcal to that of the typical steam-cracked Kuwait light naphtha shown hereinbefore.

RUN A A 200 gram portion of the above blend was admixed with 2 grams (1 wt. percent) of aluminum chloride and charged to a 1 liter round bottom flask. The admixture was-maintained for two hours in the flask at 95 F. The reaction mass was then quenched by adding 20 ml. (10 vol. percent) of a solution of l wt. percent Ethofat, a nonionic wetting agent, in distilled water, and stirring the mixture for about 30 minutes at 95 F. The aqueous phase was decanted off, the remaining mixture was agitated with 20 mil. (10 vol. percent) of 10' wt. percent sodium carbonate, and the aqueous phase was removed. The crude resinsolution lwas charged to a one liter Claisen ask equipped with a thermometer, and lthe solution was distilled to- 392 F. liquid temperature at atmospheric pressure. The overhead resin raffinate was discarded, and the remaining resin solution was then distilled to 518 F. liquid temperature at 5-6 mm. Hg.` The fiask containing the nished resin was weighed for yield determinations while still hot, after the vacuum had been released. The overhead liquid polymer or fill material was recovered and weighed. The hot, finished resin was poured into a heated ring for softening point determination.

RUN B In a second run, a 254 gram portion ofthe above blend was charged to a 30 plate Oldershaw column and fractionally distilled to 90 F at `atmospheric pressure. The fraction boiling from theinitial boiling point to 90 F. was withdrawn overhead, and the remaining 90 F.|

fractlon, amountlng to 130 grams, was recovered as bottoms. This bottoms fraction was polymerized in the same manner and under thesame conditions, described in lthe preceding paragraph. The results of the two polymerizations are compared in Table III below:

Example 2 In order to substantiate theconcl'usion that it is the 2-methyl butene-l component in a C5 resin feed whichA TABLE v Total resin, grams 75.8 Resin yield, weight percent based on feed 50.5 Liquid polymer, weight percent based on feed 10.9 Softening point CJ 77V Color b 10.5

n See footnote b, Table III. I l See footnote c, Table III'. The softening point has been lowered to the level observed in Example 1, Run A, indicating beyond ya doubt, that lit is the Z-methyl butene-I that is the degrading, undesirable component in the resin feeds.

Example 3 A steam-cracked gas oil having an initial boiling point of 100 F. and having the composition of the typical steam-cracked gas oil set forth hereinbefore in Table I was isolated. The effect of various individu-ai C5 yolefins 'f upon the resin softening point is illustrated in Table VI.

The polymerization conditions for each run were the same as in the'previous examples.

TABLE VI Rim A n o D VEy y F Feed (l) (l) (1) Olen added methyl butene-1. bmethylbutenefl. enterre-2. Zmethyl butene-2.

Weight percent o fin added Resin yield L Liquid polymer Softeniug point CJ l 1009-248o F. steam-cracked gas oil. i Weight percent based on total charge. b See footnote b, Table IH.

TABLE r11 Run o. ,l 1 2 Feed Tota-lfraction... 90 F.+fraeton. Total resins, gms S5 77.

Resin yield, VWeight percent 59.

based on feed.

Liquid polymer, weight percent based on e softening point, C.b

Color Average of several runs.

b Ring and Ball, ASTM E-28-51T.

Gardner, 20 wt. resin in xylene.

It is seen that, by removing the fraction 'boiling up to 90 F. from the resin feed, the yield and especially the softening point of the resulting resin are greatly increased. This 60-90 F. fraction was analyzed as follows:

This example conclusively illustrates that 2-methyl butenep-l' s more harmful to resin softening point than 'other'C5' olefins. Furthermore, the example shows that the adverse effect of 2methy-l butene-l increases with the amount present in the resin feed. i

I Y Example A C5 olefinic steam-cracked fraction, containing 27.3

2-methyl`butene-1, 0.4% isoprene, 'and 0.2% piperylene was dehydrogenerated at 1143 F. in the presence of the Shell catalyst (8S-90% Fe203, 58% KZCOB, 5%r r The resulting product contained 10.1% isof Cr203). prene, 12.4% piperylene, and only 13.3% 2-1nethyl butene-l. This shows that fractions containing 2-methyl butene-l may be dehydrogenated to convert the undesirable C5 olefin largely to isoprene, which is a desirable compound both in resin feeds and for other uses. Accordingly, it is contemplated as a part of thisy invention to dehydrogenate the fraction containing the 2-methyl butene-l, and to admix the resulting dehydrogenated product with the resin reed.

It is quite apparent by now that 2-methyl butene-l is a harmful component in any steam-cracked resin feed-gas oils, naphthas, and the like. The harmful effect is most noticeable when steam-cracked light naphthas :are employed as the resin feeds. 'It should be further understood that other modifications of the present invention will be obvious to those skilled in the art.

Having set forth the general nature and illustrative embodiments of the invention,.the true scope is now particularly Vpointed out in the appended claims.

What is claimed is:

1. A process for preparing petroleum resins which comprises separating a fraction containing 2methyl butene-l from a steam-cracked petroleum distillate rich in C5 unsaturated hydrocarbons aud boiling 59 l22 F. including 2methyl butene-l, and polymerizing the remaining portion of said distillate over a Friedel-Crafts catalyst to obtain a high softening point resin.

2. A process for preparing petroleum resins which comprises passing a steam-cracked petroleum distillate rich in C5 unsaturated hydrocarbons boiling 59-122 F including Z-rnethyl butene-l into a fractional distillation zone, withdrawing from said distillation zone a fraction containing the Z-methyl butene-l, contacting the remaining fractions, substantially free of Z-methyl butene-l, with a Friedel-Crafts catalyst at a temperature of 40 to 160 F., and recovering the resulting high softening point petroleum resin.

3. In a process for preparing petroleum resins wherein a steam-cracked petroleum distillate rich in C5 unsaturated hydrocarbons boiling 59 -122 F. including 2-methyl butene-l is contacted with a Friedel-Crafts polymerization catalyst at temperatures of 40 to 160 F., the improvement which comprises fractionally distilling said distillate prior to polymerization to remove the fraction containing substantially all of the 2-methyl butene-l, and polymerizing the remaining fractions in the presence of said Friedel- Crafts polymerization catalyst to produce petroleum resins of higher softening points.

4. A process according to claim 3 wherein the steamcracked petroleum distillate is a steam-cracked light naphtha distillate.

5. A process for preparing petroleum resins which comprises passing a C-CS steam-cracked petroleum fraction boiling S9 -122 F. containing Z-methyl butenel into a fractional distillation zone, distilling said fraction to remove an intermediate cut containing substantially all of the Z-methyl butene-l, passing the remaining cuts in admixture to a polymerization zone, contacting said admixture with 0.25 to 3 wt. percent of aluminum chloride at a temperature from 40 to 160 F., quenching and removing said aluminum chloride from the resulting resin solution, distilling unreacted hydrocarbons from the resin solution in an atmospheric distillation zone, distilling liquid polymer from said resin solution in a vacuum distillation zone, and recovering the high softening point resin as bottoms from said vacuum distillation zone. y

6. A process according to claim 5 wherein said intermediate cut boils from 86 to 90 F.

7. A process according to claim 5 wherein said intermediate cut is dehydrogenated at 1100 to 1225 F. in the presence of a metal oxide dehydrogenation catalyst,

and the dehydrogeuated product is polymerized with said admixture.

8. A process for preparing petroleum resins which comprises passing a steam-cracked light naphtha fraction boiling from 59 to 122 F. and containing 2-methyl butene-l into a fractional distillation zone, fractionally distilling said steam-cracked naphtha to segregate a cut boiling lbetween about 86 and 90 F. and containing substantially all of the Z-methyl butene-l present in said naphtha, recovering the remaining fractions from said distillation zone, passing the segregated 86-90 F. fraction over a metal oxide dehydrogenation catalyst at a temperature between ,1100 and 1225" F. to convert the 2-methyl butene-l present therein to more unsaturated derivatives, admixing the resulting dehydrogenated product with said remaining fractions, contacting the admixture in a polymerization zone with 0.25 to 3 wt. percent of aluminum chloride at a temperature of to 110 F. until a resin is formed, washing the aluminum chloride from the polymerization mixture, stripping the unreacted hydrocarbons and liquid polymer from said polymerization mixture, and recovering the remaining high softening point resin.

9. A process according to claim 8 wherein said steamcracked light naphtha fraction is heat-soaked to dimerize substantially all of the cyclodienes present therein, then stripped to separate an overhead product from the dimerized cyclodienes, and said overhead product is then passed to said fractional distillation zone.

10. A process for preparing petroleum resins which comprises isolating a steam-cracked petroleum distillate boiling largely above 59 F. and containing 2-methyl butene-l, separating said steam-cracked distillate into a fraction boiling 59 to 86 F., a fraction boiling 86 to 90 F. containing the 2-methyl butene-l and a fraction boiling above 90 F., mixing the 59 to 86 F. fraction with the fraction boiling above 90 F. and contacting the combined stream with 0.25 to 3% of an aluminum chloride polymerization catalyst at a temperature between 40 and 160 F. and recovering the high softening point resin produced thereby.

11. A high softening point petroleum resin produced by the process which comprises providing a C-C steam cracked light naphtha containing 2-methyl butene-l, separating the 2-methyl butene-l from said C5-CG fraction and contacting the 2-methy1 butene-l free residue with 0.25 to 3% of a Friedel-Crafts catalyst at a temperature between 40 and 160 F. until said resin is formed.

References Cited in the ile of this patent UNITED STATES PATENTS 2,750,360 Moore June 12, 1956 2,753,325 Banes et al. July 3, 1956 2,775,577 Schneider et al. Dec. 25, 1956 2,856,389 Fusco et al. Oct. 14, 1958 

3. IN A PROCESS FOR PREPARING PETROLEUM RESINS WHEREIN A STEAM-CRACKED PETROLEUM DISTILLATE RICH IN C5 UNSATURATED HYDROCARBONS BOILING 59*-122*F. INCLUDING 2-METHYL BUTENE-1 IS CONTACTED WITH A FRIEDEL-CRAFTS POLYMERIZATION CATALYST AT TEMPERATURES OF -40* TO 160*F., THE IMPROVEMENT WHICH COMPRISES FRACTIONALLY DISTILLING SAID DISTILLATE PRIOR TO POLYMERIZATION TO REMOVE THE FRACTION CONTAINING SUBSTANTIALLY ALL OF THE 2-METHYL BUTENE-1, AND POLYMERIZING THE REMAINING FRACTIONS IN THE PRESENCE OF SAID FRIEDELCRAFTS POLYMERIZATION CATALYST TO PRODUCE PETROLEUM RESINS OF HIGHER SOFTENING POINTS.
 11. A HIGH SOFTENING POINT PETROLEUM RESIN PRODUCED BY THE PROCESS WHICH COMPRISES PROVIDING A C5-C6 STEAMCRACKED LIGHT NAPHTHA CONTAINING 2-METHYL BUTENE-1 SEPARATING THE 2-METHYL BUTENE-1 FROM SAID C5-C6 FRACTION AND CONTACTING THE 2-METHYL BUTENE-1 FREE RESIDUE WITH 0.25 TO 3% OF A FRIEDEL-CRAFTS CATALYST AT A TEM- 